Roll-to-roll doping method of graphene film, and doped graphene film

ABSTRACT

The present disclosure relates to roll-to-roll doping method of graphene film, and doped graphene film.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a Continuation of International Application No.PCT/KR2010/009492 filed Dec. 29, 2010, which claims the benefits ofKorean Patent Application No. 10-2009-0134654 filed Dec. 30, 2009. Theentire disclosure of the prior application is incorporated herein byreference in its entirety.

FIELD OF THE INVENTION

The present disclosure relates to a roll-to-roll doping method of agraphene film and a graphene film doped by the method, in particular, toa roll-to-roll doping method, which includes doping the graphene film byimmersing the graphene film in a solution containing a dopant andpassing the graphene film through the solution by using a roll-to-rollprocess, a graphene film doped by the method, and a device using thesame.

BACKGROUND OF THE INVENTION

As low-dimensional nano-materials consisting of carbon atoms, there arefullerene, a carbon nanotube, graphene, graphite, and the like. That is,if carbon atoms are arranged in a hexagonal shape to form a ball shape,fullerene having a zero (0)-dimensional structure is obtained. If carbonatoms are one-dimensionally rolled, a carbon nanotube is obtained. Ifcarbon atoms form one two-dimensional atom layer, graphene is obtained.If carbon atoms are three-dimensionally stacked, graphite is obtained.

Particularly, electrical, mechanical, and chemical characteristics ofgraphene are highly stable and excellent. The graphene is a highlyconductive material, which can move electrons 100 times faster thansilicon and enable flow of about 100 times more currents than copper.The characteristics of the graphene have been verified throughexperiments since discovery of a method of isolating the graphene fromgraphite in 2004. Since then, a great deal of research on this matterhas been carried out.

Since the graphene is composed of only carbons, which are relativelylight atoms, it facilitates processing of a one- or two-dimensionalnanopattern. By using the graphene, semiconductive-conductive propertiescan be adjusted. By using diversity of chemical bonds of carbons,wide-range functional devices such as sensors and memories can befabricated.

However, due to lack of a method for effective synthesis, transfer, anddoping, quality and a scale required to actually produce a graphene filmhave been restricted. For example, a conventional transparent electrode,such as an indium tin oxide (ITO), which is generally used for a solarcell, exhibits unlimited scalability, ˜90% of optical transparency, anda sheet resistance smaller than 100 Ohm/square. However, the highestrecords of the graphene film still remain about ˜500 Ohm/square of sheetresistance, ˜90% of transparency, and a scale of several centimeters.

In order to solve the problems, the present disclosure provides aroll-to-roll doping method of a graphene film, which includes doping thegraphene film by immersing the graphene film in a doping solutioncontaining a dopant and passing the graphene film through the solution,or passing the graphene film through a dopant vapor generated byvaporizing the doping solution by using a roll-to-roll process, agraphene film doped by the method, and a roll-to-roll doping apparatusof a graphene film.

However, problems sought to be solved by the present disclosure are notlimited to the above-described problems. Other problems to be solved bythe present disclosure, which are not described herein, can be clearlyunderstood by those skilled in the art from the descriptions below.

BRIEF SUMMARY OF THE INVENTION

In order to accomplish the above-described object, one aspect of thepresent disclosure provides a roll-to-roll doping method of a graphenefilm, which includes doping the graphene film by passing the graphenefilm through a doping solution containing a dopant or a dopant vapor, byusing a roll-to-roll process.

Another aspect of the present disclosure provides a doped graphene filmformed by the doping method of the illustrative embodiment.

Another aspect of the present disclosure provides a device including thedoped graphene film formed by the doping method of the illustrativeembodiment.

Another aspect of the present disclosure provides a roll-to-roll dopingapparatus including: a first roller unit that forms a layered structureincluding a substrate-graphene film-first flexible substrate; a secondroller unit that removes the substrate from the layered structure byimmersing the layered structure provided by the first roller unit in anetching solution and transfers the graphene film on the first flexiblesubstrate at the same time; a third roller unit that transfers thegraphene film transferred to the first flexible substrate on a secondflexible substrate; and a fourth roller unit that dopes the graphenefilm by passing the graphene film through a doping solution or a dopantvapor and that is placed between the second roller unit and the thirdroller unit, or next to the third roller unit.

In accordance with the present disclosure, a large scale graphene filmcan be easily doped by the roll-to-roll process. Through theroll-to-roll process, it is possible to provide a method enabling dopingof graphene itself by transferring and stacking at least two layers ofthe graphene film.

The graphene film doped by the doping method of the present disclosuremay improve an electrical characteristic, sheet resistance, andtransparency. Accordingly, the graphene film doped by the roll-to-rollprocess can be used in fabricating various devices. For example, thegraphene film doped by the roll-to-roll process may be used as anelectrode material or the like for various devices.

BRIEF DESCRIPTION OF THE DRAWINGS

Non-limiting and non-exhaustive embodiments will be described inconjunction with the accompanying drawings. Understanding that thesedrawings depict only several embodiments in accordance with thedisclosure and are, therefore, not to be intended to limit its scope,the disclosure will be described with specificity and detail through useof the accompanying drawings, in which:

FIG. 1 is a schematic view showing a roll-to-roll doping apparatus of agraphene film and a roll-to-roll doping method of a graphene film usingthe apparatus in accordance with an illustrative embodiment;

FIG. 2 is a schematic view showing a roll-to-roll doping andtransferring method of a graphene film in accordance with anillustrative embodiment;

FIG. 3 is a cross-sectional view showing a roll-to-roll doping andtransferring method of a graphene film in accordance with anillustrative embodiment;

FIG. 4 is a cross-sectional view showing a roll-to-roll doping andtransferring method of a graphene film in accordance with anotherillustrative embodiment;

FIG. 5 is a graph showing a Raman spectrum of a doped graphene film anda X-ray photoelectron spectrum (XPS) expanded by doping in accordancewith an example of an illustrative embodiment;

FIG. 6 is a graph showing an electrical characteristic of layer-by-layertransferred and doped graphene films in accordance with an example of anillustrative embodiment;

FIG. 7 is a graph obtained from measuring a decrease of sheet resistanceof a graphene film doped by varying dopants in accordance with anexample of an illustrative embodiment;

FIG. 8 is a graph showing relation between a decrease of sheetresistance and transparency depending on variation of concentration of adopant in accordance with an example of an illustrative embodiment; and

FIG. 9 is a graph showing relation between a decrease of sheetresistance and transparency depending on a doping time in accordancewith an example of an illustrative embodiment.

DETAILED DESCRIPTION OF THE INVENTION

Hereinafter, illustrative embodiments and examples will be described indetail with reference to the accompanying drawings so that the inventiveconcept may be readily implemented by those skilled in the art.

However, it is to be noted that the present disclosure is not limited tothe illustrative embodiments, and can be realized in various other ways.In the drawings, certain parts not directly relevant to descriptions ofthe present disclosure are omitted to enhance the clarity of thedrawings. Throughout the whole document, like reference numerals denotelike parts.

Throughout the whole document, the term “on” that is used to designate aposition of one element with respect to another element includes both acase that the one element is adjacent to the another element and a casethat any other element exists between these two elements. Further, theterm “comprises or includes” and/or “comprising or including” used inthe document means that one or more other components, steps, operationand/or existence or addition of elements are not excluded in addition tothe described components, steps, operation and/or elements unlesscontext dictates otherwise.

The terms “about or approximately” or “substantially” are intended tohave meanings close to numerical values or ranges specified with anallowable error and intended to prevent accurate or absolute numericalvalues disclosed for understanding of the present disclosure from beingillegally or unfairly used by any unconscionable third party.

Throughout the whole document, the term “graphene film” means a layer orsheet form of graphene, in which multiple carbon atoms are covalentlybonded to one another, thereby forming polycyclic aromatic molecules.The covalently bonded carbon atoms form a 6 circular ring as a basicrepeat unit, but may further include 5 and/or 7 circular rings.Accordingly, the graphene layer appears to be a monolayer of thecovalently bonded carbon atoms (in general, sp² bond). The graphenelayer may have various structures. The structure of the graphene layermay vary depending on a content of the 5 and/or 7 circular rings thatmay be included in the graphene. The graphene layer may be formed of amonolayer of graphene as described above, but several graphene layersmay be stacked, thereby forming multiple layers. In general, a side endpart of the graphene may be saturated with hydrogen atoms.

Throughout the whole document, the term “roller unit” means a device ina roll-to-roll form, which is composed of one roller or multiplerollers, and is not limited with respect to a shape, a size, and/or anarrangement form of a roller.

A roll-to-roll doping method of a graphene film in accordance with oneaspect of the present disclosure includes doping the graphene film bypassing the graphene film through a doping solution containing a dopantor a dopant vapor, by using a roll-to-roll process. More specifically,the graphene film can be doped through contact with a dopant gas byimmersing the graphene film in a solution containing a dopant andpassing the graphene film through the solution by using the roll-to-rollprocess, or passing the graphene film through a dopant vapor generatedby vaporizing the doping solution by using the roll-to-roll process.

In an illustrative embodiment, the roll-to-roll doping method of thegraphene film includes: forming a layered structure including asubstrate-graphene film-first flexible substrate from the graphene filmformed on a substrate and the first flexible substrate in contact withthe graphene film by a first roller unit; immersing the layeredstructure in an etching solution and passing the layered structurethrough the etching solution by using a second roller unit to remove thesubstrate from the layered structure and to transfer the graphene filmon the first flexible substrate at the same time; and transferring thegraphene film transferred on the first flexible substrate on a secondflexible substrate by using a third roller unit, wherein the graphenefilm is doped by a fourth roller unit by passing the graphene filmthrough the doping solution containing a dopant or a dopant vapor aftertransferring the graphene film on the first flexible substrate or aftertransferring the graphene film on the second flexible substrate.However, the illustrative embodiment is not limited thereto.

In an illustrative embodiment, the substrate may have one or morecharacteristics of transparency, flexibility, and extendibility.However, the illustrative embodiment is not limited thereto.

In an illustrative embodiment, the dopant may include an organic dopant,an inorganic dopant, or their combination. However, the illustrativeembodiment is not limited thereto.

In an illustrative embodiment, the dopant may include at least oneselected from the group consisting of an ionic liquid, an ionic gas, anacidic compound, an organic compound, and an organic polymeric compound.For example, the dopant may include at least one selected from the groupconsisting of NO₂BF₄, NOBF₄, NO₂SbF₆, HCl, H₂PO₄, CH₃COOH, H₂SO₄, HNO₃,PVDF, Nafion, AuCl₃, SOCl₂, Br₂, CH₃NO₂, dichlorodicyanoquinone, oxone,dimyristoylphosphatidylinositol, and trifluoromethanesulfonimide.However, the illustrative embodiment is not limited thereto. Thesolution containing the dopant is contained in a vessel (notillustrated).

In an illustrative embodiment, the roll-to-roll doping method of thegraphene film may include performing stacking an additional graphenefilm on the doped graphene film to form a multilayer graphene film, anddoping the multilayer graphene film by using the roll-to-roll dopingmethod of the graphene film, in turn at least one time. However, theillustrative embodiment is not limited thereto.

In an illustrative embodiment, the graphene film is transferred andstacked to form at least two layers by using the roll-to-roll processsuch that the graphene itself can be doped.

In an illustrative embodiment, the roll-to-roll method of the graphenefilm may include performing one or more times of a process includingstacking an additional graphene film on the doped graphene film anddoping the stacked graphene film by the roll-to-roll doping method.However, the illustrative embodiment is not limited thereto.

In an illustrative embodiment, the roll-to-roll method of the graphenefilm may further include forming a protective layer on the dopedgraphene film by using a fifth roller unit. However, the illustrativeembodiment is not limited thereto.

In an illustrative embodiment, the roll-to-roll method of the graphenefilm may further include a process of cleaning and/or drying the dopedgraphene film. However, the illustrative embodiment is not limitedthereto.

In an illustrative embodiment, the first and second flexible substratesmay include polymers, respectively. However, the illustrative embodimentis not limited thereto. For example, the first and second flexiblesubstrates may be thermal release polymers, respectively.

In an illustrative embodiment, the graphene film may be formed on asubstrate. The substrate may have at least one characteristic oftransparency, flexibility, and extendibility. However, the illustrativeembodiment is not limited thereto.

In an illustrative embodiment, the substrate may further include acatalyst layer. However, the illustrative embodiment is not limitedthereto. For example, the substrate or the catalyst layer on thesubstrate may independently include at least one metal or alloy selectedfrom the group consisting of Ni, Co, Fe, Pt, Au, Al, Cr, Cu, Mg, Mn, Mo,Rh, Si, Ta, Ti, W, U, V, Zr, brass, bronze, white brass, stainlesssteel, and Ge. However, the illustrative embodiment is not limitedthereto.

In an illustrative embodiment, the graphene film may include a monolayeror a multilayer graphene. As an unlimited example, thickness of thegraphene film can be adjusted in a range of about 1 to about 50 layers.If more layers of graphene than the above range are formed, a physicalproperty of graphite, and not a physical property of graphene itself,may be obtained.

In an illustrative embodiment, the graphene film formed on the substratemay be formed by supplying heat and a reaction gas containing a carbonsource to the substrate to grow graphene on the substrate. However, theillustrative embodiment is not limited thereto.

In an illustrative embodiment, the doped graphene film may have a rollshape, a foil shape, a tube shape, a plate shape, a sheet shape or awire shape. However, the illustrative embodiment is not limited thereto.

Another aspect of the present disclosure provides a graphene film dopedby the doping method of the illustrative embodiment.

Another aspect of the present disclosure provides a device including thegraphene film doped by the doping method of the illustrative embodiment.All the descriptions of the roll-to-roll doping method of the graphenefilm may be applied to the doped graphene film, and the device includingthe doped graphene film. For convenience, overlapping descriptions areomitted.

The roll-to-roll doping apparatus of graphene in accordance with anotheraspect of the present disclosure includes: a first roller unit thatforms a layered structure including a substrate-graphene film-firstflexible substrate; a second roller unit that removes the substrate fromthe layered structure by immersing the layered structure provided by thefirst roller unit in an etching solution and transfers the graphene filmon the first flexible substrate at the same time; a third roller unitthat transfers the graphene film transferred on the first flexiblesubstrate on a second flexible substrate; and a fourth roller unit thatdopes the graphene film by passing the graphene film through a dopingsolution or a dopant vapor and that is placed between the second rollerunit and the third roller unit, or next to the third roller unit.

Hereinafter, the roll-to-roll doping method of the graphene film, thedoped graphene film, and the graphene roll-to-roll doping apparatus inaccordance with the present disclosure will be described in detail withreference to the drawings. However, the present disclosure is notlimited thereto.

FIG. 1 shows the roll-to-roll doping apparatus of the graphene film andthe roll-to-roll doping method of the graphene film using the apparatus.With reference to FIG. 1, the doping apparatus of the graphene film 20in accordance with the present disclosure may include: a first roller 3that provides the graphene film into a doping solution or a dopantvapor; a second roller 4 that immerses the graphene film provided by thefirst roller in the doping solution or passes the graphene film providedby the first roller through the dopant vapor; and a third roller 5 thatdischarges the graphene film, which has passed through the dopingsolution and been doped by the second roller, out of the vesselcontaining the doping solution or the dopant vapor.

The roll-to-roll doping apparatus of the graphene film may furtherinclude a roller (not illustrated) that performs a screen printingprocess to improve adhesion of the graphene film prior to and after thedoping. Specifically, the rollers may be added to the first roller 3 andthe third roller 5, respectively. Accordingly, when the graphene filmpasses through the first roller 3 and the third roller 5, a protectivelayer may be inserted so as to minimize scratch and damage of thegraphene. Since the first roller 3 and the third roller 5 contactdirectly with the graphene, the first roller and the third roller causescratches thereby resulting in damage to the graphene surface when therollers are immersed in the doping solution (or come out of the dopingsolution). Accordingly, soft graphene protective layers (PET, PTFE, andPVDF, etc.) may be inserted into the first roller 3 and the third roller5, respectively, so as to minimize scratch and damage of the graphene,and improve adhesion between the graphene and a target substrate. Tothis end, the roll-to-roll doping apparatus of the graphene film mayfurther include the roller for performing the screen printing process.Materials for the protective layers are not limited. For example, theprotective layers may include poly methyl methacrylate (PMMA),photoresist (PR), electron resist (ER), SiOx, and AlOx. However, theillustrative embodiment is not limited thereto.

The graphene film may be a graphene film doped with an organic dopantand/or an inorganic dopant. For example, the dopant may include at leastone selected from the group consisting of an ionic liquid, an ionic gas,an acidic compound, and an organic compound. The dopant may include atleast one selected from the group consisting of NO₂BF₄, NOBF₄, NO₂SbF₆,HCl, H₂PO₄, CH₃COOH, H₂SO₄, HNO₃, PVDF, Nafion, AuCl₃, SOCl₂, Br₂,CH₃NO₂, dichlorodicyanoquinone, oxone, dimyristoylphosphatidylinositol,and trifluoromethanesulfonimide. However, the illustrative embodiment isnot limited thereto.

If the dopant vapor is used during the doping process, the dopant vapormay be formed by a heating device for vaporizing the doping solution ina vessel containing the doping solution. If the doping solution is usedduring the doping process, a vessel provided with a height adjustmentdevice to adjust an interval between the graphene film and the dopantsolution may be used as the vessel containing the doping solution.

During the doping process, the characteristics of the doped graphenefilm, which is formed through the doping process, can be adjusted byvarying the dopant and/or a doping time. For example, sheet resistanceand transparency of the doped graphene film can be adjusted by varyingthe dopant and/or the doping time.

FIG. 2 shows a roll-to-roll transferring and doping method of thegraphene film formed on a substrate. More specifically, the method fordoping the graphene film on the substrate may include: (S1) forming alayered structure 50 including a substrate 10-graphene film 20-firstflexible substrate 31 from the graphene film 20 formed on a substrate 10and the first flexible substrate 31 in contact with the graphene film bya first roller unit 110; (S2) immersing the layered structure in anetching solution and passing the layered structure through the etchingsolution by using a second roller unit 120 to remove the substrate 10from the layered structure 50 and to transfer the graphene film 20 onthe first flexible substrate 31 at the same time; and (S3) transferringthe graphene film transferred on the first flexible substrate on asecond flexible substrate 32 by using a third roller unit 130, whereinthe graphene film is doped by a fourth roller unit 140 after (S2)transferring the graphene film on the first flexible substrate or after(S3) transferring the graphene film on the second flexible substrate.For example, the first roller unit may be an adhesive roller and thesecond and third roller units may be transfer rollers. However, theillustrative embodiment is not limited thereto. With reference to FIGS.3 and 4, the doping process may be performed after S2 as illustrated inFIG. 3 or after S3 as illustrated in FIG. 4. If necessary, theroll-to-roll doping method of the graphene film may further include aprocess for cleaning and/or drying the doped graphene film. However, theillustrative embodiment is not limited thereto.

More specifically, in S1, the first flexible substrate 31 is in contactwith the graphene film formed on the above-described substrate andprovided to the first roller unit 110. The first flexible substrate mayfurther include an adhesive layer formed thereon to facilitate transferof the graphene film from the substrate. Materials for the adhesivelayer are not limited. Any materials can be used if they are generallyused by those skilled in the art to facilitate the transfer. Forexample, the adhesive layer may include an adhesive tape, a glue, anepoxy resin, a photosoftning tape (UV visible light, an electron beam,and UV/EB), a thermal release tape, a water-soluble tape and the like.However, the illustrative embodiment is not limited thereto.

Through the above-described method, the graphene layer 20 on thesubstrate 10 and the first flexible substrate 31 are in contact witheach other and pass through the first roller unit 110, so that a layeredstructure 50 of the metal substrate-graphene layer-first flexiblesubstrate is formed. Thereafter, a cooling or plasma process for thelayered structure may be further performed as a pre-treatment processbefore the layered structure is provided to the second roller unit 120.The first roller unit 110 may be composed of a pair of a lower rollerand an upper roller, which are facing to each other, as illustrated inFIG. 3. If necessary, however, multiple rollers may be further includedin the first roller unit. For example, if the process of S1 islengthened, in order to prevent downward bending or drooping of thegraphene layer on the metal substrate to be introduced, the firstflexible substrate, or the layered structure, multiple rollers may befurther included.

Subsequently, the layered structure 50 is immersed in the etchingsolution 60 and pass through the etching solution 60 by using the secondroller unit 120 so that the substrate is removed from the layeredstructure, and the graphene film is transferred on the first flexiblesubstrate at the same time (S2). The etching solution is an aqueoussolution, which is capable of selectively etching only a substrate or asubstrate containing a catalyst layer. For example, the etching solutionmay be a solution containing ammonium persulfate (NH₄)₂S₂O₈, HF, BOE,Fe(NO₃)₃, iron chloride (Iron(III) Chloride, FeCl₃), CuCl₂, or others.However, the illustrative embodiment is not limited thereto. The etchingsolution may be selected depending on a type of a substrate. Forexample, if the substrate is Ni or Cu, the etching process may beperformed by FeCl₃. In addition to the above-described etching method,reaction ion etching, ion milling, ashing, or others may be used toremove the substrate.

The process for removing the metal substrate through the etching processmay be performed one time or several times, if necessary. For example,the etching process may be performed one time, or several times by thesecond roller unit 120 as illustrated in FIG. 3. With reference to FIG.3, in the etching process, multiple rollers are repeatedly arranged inupper and lower portions of a chamber such that the layered structurecan be immersed in the etching solution several times and pass throughthe solution. By repeatedly performing the etching process severaltimes, the substrate that the layered structure contains or thesubstrate containing the catalyst layer can be more thoroughly removed.

If the flexible substrate is a thermal release polymer, heat processingmay be performed simultaneously with the rolling process so that thegraphene film can be easily detached from the flexible substrate.Through the heat processing, transferring and doping of a large scalegraphene film can be more easily performed in a short time with lowcosts.

Here, the substrate 10 may exist solely or further contain a catalystlayer (not illustrated). Materials for the substrate are not limited.For example, the substrate may include at least one metal or alloyselected from the group consisting of Ni, Co, Fe, Pt, Au, Al, Cr, Cu,Mg, Mn, Mo, Rh, Si, Ta, Ti, W, U, V, Zr, brass, bronze, white brass,stainless steel, and Ge. If the substrate is a metal, the metalsubstrate may function as a catalyst to form the graphene film. However,the substrate does not have to be a metal. For example, silicon may beused for the substrate. In order to form a catalyst layer on the siliconsubstrate, a substrate, on which a silicon oxide layer is further formedthrough oxidization of the silicon substrate, may be used.

In order to facilitate growth of the graphene film 20 on the substrate10, a catalyst layer may be further formed thereon. Materials,thickness, and a shape of the catalyst layer are not limited. Forexample, the catalyst layer may be at least one metal or alloy selectedfrom the group consisting of Ni, Co, Fe, Pt, Au, Al, Cr, Cu, Mg, Mn, Mo,Rh, Si, Ta, Ti, W, U, V, Zr, brass, bronze, white brass, stainlesssteel, and Ge. The catalyst layer may be formed of materials identicalor different from those of the substrate. The thickness of the catalystlayer is not limited. The catalyst layer may be a thin or thick film.

As the method for forming the graphene film 20 on the substrate 10, achemical vapor deposition method, which is generally used in the art ofthe present disclosure to grow the graphene, may be used withoutlimitation. For example, the chemical vapor deposition method mayinclude rapid thermal chemical vapor deposition (RTCVD), inductivelycoupled plasma-chemical vapor deposition (ICP-CVD), low pressurechemical vapor deposition (LPCVD), (atmospheric pressure chemical vapordeposition (APCVD), metal organic chemical vapor deposition (MOCVD), orplasma-enhanced chemical vapor deposition (PECVD). However, theillustrative embodiment is not limited thereto.

As an example for forming the graphene film on the substrate, a reactiongas containing a carbon source and heat may be supplied to the substratecontaining a catalyst so as to form the graphene film. For example, aquartz tube reactor having an 8-inch diameter may be introduced into aCVD system. In this case, for example, a monolayer graphene film may beformed on a large scale Cu foil roll having an about 30-inch diagonallength. Generally, a temperature gradient within a tube-shaped reactoris large in a radiation direction. Accordingly, the graphene growth onthe Cu foil becomes ununiformed. In order to solve the problem, forexample, a ˜7.5 inch quartz tube wrapped with the Cu foil is insertedinto a ˜8 inch quartz tube and fixed therein. Accordingly, theununiformity in the radiation direction at a reaction temperature can beminimized.

The process for growing the graphene film 20 may be performed atatmospheric pressure, a low pressure, or under vacuum. For example, ifthe process is performed under the condition of atmospheric pressure,helium (He) or the like may be used as a carrier gas to minimize damageto the graphene caused by collision with heavy argon (Ar) at a hightemperature. Also, if the process is performed under the condition ofatmospheric pressure, the large scale graphene film can be made througha simple process with low costs. If the process is performed under thecondition of the low pressure or vacuum, hydrogen (H₂) may be used as anatmosphere gas while increasing a temperature, so that an oxidizedsurface of a metal catalyst is reduced, and high quality graphene can besynthesized.

The graphene film 20 formed by the above-described method may have alarge scale with a horizontal or vertical length of more than about 1 mmto about 1,000 m. The graphene film 20 includes a graphene film havinglittle deficits, i.e., a homogeneous structure. The graphene film formedby the above-described method may include monolayer or multilayergraphene. As an unlimited example, thickness of the graphene film may beadjusted in a range of about 1 or about 50 layers.

In the illustrative embodiment for forming the graphene film 20 on thesubstrate 10, the graphene film is grown by putting the metal substratein a roll form into a tube-shaped furnace, supplying a reaction gascontaining a carbon source, and performing heat processing atatmospheric pressure, and the layered structure 50 of the metalsubstrate-graphene film-first flexible substrate is formed by contactingthe graphene film 20 formed on the metal substrate with the firstflexible substrate 31 by using the first roller unit 110. If a heatprocessing is performed in a range of, for example, from about 300° C.to about 2000° C. while the carbon source such as carbon monoxide,carbon dioxide, methane, ethane, ethylene, ethanol, acetylene, propane,butane, butadiene, pentane, pentene, cyclopentadiene, hexane,cyclohexane, benzene, toluene is supplied in the form of gas, carboncomponents contained in the carbon source are combined with each otherto form a hexagonal plate structure and the graphene layer can be grown.

As described above, the roll-to-roll transferring method of the graphenefilm enables transfer and doping of the graphene film on varioussubstrates with low costs through a simple process. Since the graphenehas high transparency, it may be applied to fabricating variouselectrical and electronic devices. Especially, the graphene may beeffectively used in fabricating electrodes of various electrical andelectronic devices. For example, it is possible to realize effectiveutilization of graphene transparent electrodes for photoelectromagneticapplication in fabricating electrodes of various electrical andelectronic devices such as a next-generation field effect transistorrequiring flexibility and/or extendibility, or a diode, or in the fieldof a solar cell, a touch sensor, and related flexible electronictechnologies. Through the doping process by the roll-to-roll process,the electrical characteristic of the graphene film is improved. Further,sheet resistance and transparency, which are equivalent to recentcommercial transparent electrodes such as indium tin oxide, can beexhibited.

Hereinafter, examples for the roll-to-roll doping method of the graphenefilm and the graphene film formed by the method in accordance with thepresent disclosure will be described in detail with reference to thedrawings. However, the present disclosure is not limited thereto.

Example 1 1. Growth of a Large Scale Graphene Film on a Copper Foil

A ˜7.5 inch quartz tube was wrapped with a Cu substrate (thickness: 25μm; size: 210×297 mm²; Alfa Aesar Co.) to form a roll of the Cusubstrate. The quartz tube was inserted into a ˜8 inch quartz tube andfixed therein. Thereafter, the quartz tube was heated to 1,000° C. whileflowing 10 sccm H₂ at 180 mTorr. After the temperature of the quartztube reaches 1,000° C., annealing was performed for 10 minutes whilemaintaining the hydrogen flow and the pressure. Subsequently, a gasmixture (CH₄:H₂=30:10 sccm) containing a carbon source was supplied at1.6 Torr for 15 minutes such that graphene was grown on the Cusubstrate. Thereafter, the graphene was cooled to a room temperature ata rate of 10° C./s within a short time while flowing H₂ at a pressure of180 mTorr. As a result, a graphene film grown on the Cu substrate wasobtained.

2. A Chemical Doping Method of a Graphene Film

Resistivity may be presented by the formula of ρ=1σ (or 1/neμ). In orderto improve conductivity, there is a method of increasing mobility (μ) ora carrier concentration. If doping is performed through chemicaltreatment, conductivity can be improved by increasing the carrierconcentration. If AuCl₃ is used as a dopant, the doping principle of thegraphene is that Au³⁺ ions dissolved in a salt state in a solutionreceive electrons from the surface of the graphene film so that Auparticles are formed on the surface of the graphene. Accordingly, the Auparticles take the electrons from the graphene so that strong p-dopingoccurs. As identified from the graphene band structure, a Fermi leveldecreases, thereby increasing the carrier concentration. According tothe formula of σ=neμ, the conductivity is improved.

With respect to leading analysis methods to measure a degree of dopingof the graphene, there are three methods as set forth hereinafter.Firstly, the carrier concentration and a degree of variation of a Diracpoint can be identified through fabrication of a hall bar device. If theRaman analysis method is used, a degree of p-type doping and n-typedoping can be qualitatively identified through intensity of a peak and ashift direction. In case of the p-type doping, blue shift of G- and2D-band peaks occurs, and intensity of the 2D-band peak tends to beweakened. In case of the n-type doping, red shift of the G-band peakoccurs, and blue shift of the 2D-band peak occurs. If XPS is used,absorption materials on the surface of the graphene can be sorted, and adegree of doping can be identified through a shift direction andintensity of a C1s peak.

3. Transfer and Roll-to-Roll Doping Process of a Graphene Film

A thermal release tape (Jin Sung Chemical Co. and Nitto Denco Co.) wascontacted with the graphene film formed on the Cu substrate, andthereafter, was passed through the adhesive roller including two rollerswhile applying a weak pressure of ˜2 MPa so that the graphene film wasadhered on the thermal release tape. Next, the layered structure of Cusubstrate/graphene film/thermal release tape was immersed in a 0.5 MFeCl₃ or 0.15 M (NH₄)₂S₂O₈ etching aqueous solution to etch and removethe Cu substrate through electro-chemical reaction so that a layeredstructure of the graphene film/the thermal release tape was obtained.Thereafter, the graphene film was cleaned with deionized water to removeresidual etching components. Next, a target substrate was contacted withthe graphene film transferred to the thermal release tape. Thereafter,the target substrate and the graphene film passed through the transferroller while applying low heat of 90˜120° C. for ˜5 minutes. As aresult, the graphene film was transferred from the thermal release tapeon the target substrate. If necessary, the above-described processes maybe repeatedly performed on the same target substrate, so that amultilayer graphene film can be transferred on the target substrate. Asthe target substrate, for example, polyethylene terephthalate (PET)having a 34-inch scale in a diagonal direction and thickness of 188 μmmay be used.

Subsequently, at least one layer of the graphene film transferred on thetarget substrate was doped through the roll-to-roll process as shown inthe above-described embodiments and FIGS. 1 to 4. Specifically, thegraphene film was p-doped by immersing at least one layer of thegraphene film transferred on the target substrate in a solutioncontaining 63 wt % HNO₃ for about 5 minutes and passing the graphenefilm through the solution by using the roll-to-roll transferring deviceas shown in FIG. 1.

FIG. 5 shows a Raman spectrum (on SiO₂ (300 nm)/Si) of the p-dopedgraphene film transferred to the PET target substrate roll having thethickness of 188 μm in accordance with the example of the illustrativeembodiment, and a X-ray photoelectron spectrum (XPS) showing red-shiftand peak broadening by the p-doping. FIG. 5A is a Raman spectrum of aHNO₃-doped graphene film, showing ˜18 cm⁻¹ blue shift of both the G and2D peaks. Here, a D band peak was not observed prior to and after thedoping. This means that the HNO₃ treatment does not break the chemicalbond of the graphene. FIG. 5B is an X-ray photoelectron spectrum (XPS)showing typical red-shift and peak broadening by the p-doping. Thespectrum may be understood as re-hybridization of molecule orbitals intoan intermediate state between sp² and sp³.

Due to the unique electronic band structure of the graphene, chargecarrier density significantly increases through the p or n-doping,thereby resulting in improvement of the sheet resistance. The inventorsof the present disclosure attempted various types of chemical dopingmethods useful for the carbon nanotube. They discovered that a nitricacid (HNO₃) is effective for the p-doping of the graphene film. FIG. 5Ashows a Raman spectrum of the graphene film prior to and after dopingwith 63 wt % (16 M) HNO₃ for 5 minutes. A large peak displacement (Δν=18cm⁻¹) indicates that the graphene film is strongly p-doped. Asillustrated in FIG. 5A, the shifted G peak implies appearance of anadditional vibration mode caused by the strong p-doping. In X-rayphotoelectron spectrum data (FIG. 5B), a new peak is observed betweensatellite peaks of C1s corresponding to the sp² and sp³ hybridizationstate. This indicates variation of the electron structure of thegraphene resulting from the strong doping effect.

FIG. 6 is a graph showing an electrical characteristic of layer-by-layertransferred and doped graphene film in accordance with the example ofthe illustrative embodiment. FIG. 6A is a graph for the sheet resistanceof the graphene film transferred by using a roll-to-roll dry transfermethod combined with the thermal release tape and a PMMA-based wettransfer method. FIG. 6B is a graph showing an electrical characteristicof a monolayer graphene hall bar device in vacuum. With respect to FIG.6B, 4-point resistivity was measured as a function of a back gatevoltage (Vg) in a device at a room temperature and T=6K. A quantum Halleffect (QHE) was measured in the same device under a very lowtemperature (T=6K) and a high magnetic field (B=9T). Longitudinalresistivity ρxx and hall conductivity oxy were presented as a functionof a gate voltage. It is observed that a sequence of three half-integerplateaus corresponding to υ=2, 6, and 10, which are typical for themonolayer graphene, was clearly presented. The Hall effect mobility ofthe device exhibits μHall=7,350 cm²V⁻¹s⁻¹ (˜5,100 cm²V⁻¹s⁻¹ at 295 K) at6K. This shows that the quality of the graphene formed by CVD also hasan excellent electrical characteristic equivalent to that of thegraphene mechanically released from graphite.

P-doping with HNO₃ apparently improves the electrical characteristic ofthe graphene film, and is more effective for the roll-to-roll producedgraphene. The graphene film obtained by stacking 4 layers of a graphenefilm through the layer-by-layer transferring and doping method exhibitedaverage 90% optical transparency. The sheet resistance of the graphenefilm was improved from 250 Ω/sq to finally 35 Ω/sq for the monolayer.Accordingly, a highly conductive transparent electrode was produced.Since the transparent electrode is flexible while having opticaltransmittance and an electrical sheet resistance value, which arecomparable with those of ITO, it is expected that many researches as anew material will be performed in various application fields of atransparent electrode.

FIG. 7 and Table 1 below provide results showing sheet resistancedecrease and transparency in the case where the graphene film was dopedby varying doping materials for the graphene film.

TABLE 1 Resistance Dopant No. Decrease (%) Transparency (%) (+OrganicSolvent) 1 28.5 97.6 Nitromethane 2 58 96.1 HNO₃ (16M) 3 65 96.5 HNO₃ +Nitromethane (0.025 mM) 4 85.9 87.1 AuCl₃ + Nitromethane (0.025 mM) 5 4897.2 HAuCl₄ + DI (80 mM) 6 74 97 HAuCl₄ + DI + Nitromethane (0.025 mM) 73 81 H₂SO₄ (16 mM) 8 13 82.4 H₂SO₄ + Nitromethane (0.025 mM) 9 69 95.3HCl 10 47 96.3 HCl + Nitromethane (0.025 mM) 11 −40 85 H₃PO₄

FIGS. 8 and 9 are graphs obtained from observation of sheet resistanceand transparency by varying conditions such as a concentration of adopant and a doping time in case of performing doping through theroll-to-roll doping method of an illustrative embodiment, and by usingAuCl₃ as a dopant and nitromethane as an organic solvent.

With reference to FIG. 8, decrease of sheet resistance and transparencyof the doped graphene film were observed by using AuCl₃ as a dopant andnitromethane as an organic solvent, and varying the concentration in arange of from 0.01 M to 0.1 M. As the concentration of the AuCl₃ dopantincreases, the decrease of the sheet resistance increased from about 46%to about 88%. However, the transparency decreased from about 82% to 54%.

With reference to FIG. 9, the graph was obtained by observing the sheetresistance and the transparency by using AuCl₃ as a dopant andnitromethane as an organic solvent, and maintaining a concentration of0.025 mM. As the doping time increases, the transparency constantlydecreases. However, the decrease of the sheet resistance tended toincrease up to about 5 minutes, and thereafter, slightly decreased.

The above description of the illustrative embodiments is provided forthe purpose of illustration, and it would be understood by those skilledin the art that various changes and modifications may be made withoutchanging technical conception and essential features of the illustrativeembodiments.

1. A roll-to-roll doping method of a graphene film, comprising: dopingthe graphene film by passing the graphene film through a doping solutioncontaining a dopant or a dopant vapor using roll-to-roll process.
 2. Theroll-to-roll doping method of the graphene film of claim 1 including:forming a layered structure including a substrate-graphene film-firstflexible substrate from the graphene film formed on a substrate and thefirst flexible substrate in contact with the graphene film by a firstroller unit; immersing the layered structure in an etching solution andpassing the layered structure through the etching solution by using asecond roller unit to remove the substrate from the layered structureand to transfer the graphene film on the first flexible substrate at thesame time; and transferring the graphene film transferred on the firstflexible substrate on a second flexible substrate by using a thirdroller unit, wherein the graphene film is doped by a fourth roller unitby passing the graphene film through the doping solution containing adopant or a dopant vapor after transferring the graphene film on thefirst flexible substrate or after transferring the graphene film on thesecond flexible substrate.
 3. The roll-to-roll doping method of thegraphene film of claim 2, wherein the graphene film formed on thesubstrate is formed by supplying heat and a reaction gas containing acarbon source to the substrate to grow graphene on the substrate.
 4. Theroll-to-roll doping method of the graphene film of claim 2, wherein thesubstrate has one or more characteristics of transparency, flexibility,and extendibility.
 5. The roll-to-roll doping method of the graphenefilm of claim 2, wherein the substrate further comprises a catalystlayer.
 6. The roll-to-roll doping method of the graphene film of claim 1including: performing one or more times of a process including stackingan additional graphene film on the doped graphene film and doping thestacked graphene film by the roll-to-roll doping method.
 7. Theroll-to-roll doping method of the graphene film of claim 1, wherein thegraphene film includes a monolayer graphene or a multilayer graphene. 8.The roll-to-roll doping method of the graphene film of claim 1, whereinthe dopant includes an organic dopant, an inorganic dopant or theircombination.
 9. A doped graphene film formed by a roll-to-roll dopingmethod of claim
 1. 10. The doped graphene film of claim 9, wherein thegraphene film is doped with an organic dopant, an inorganic dopant ortheir combination.
 11. The doped graphene film of claim 9, wherein thedopant includes at least one selected from the group consisting of anionic liquid, an ionic gas, an acidic compound, and an organic polymericcompound.
 12. The doped graphene film of claim 9, Wherein the dopantincludes at least one selected from the group consisting of NO₂BF₄,NOBF₄, NO₂SbF₆, HCl, H₂PO₄, CH₃COOH, H₂SO₄, HNO₃, PVDF, Nafion, AuCl₃,SOCl₂, Br₂, CH₃NO₂, dichlorodicyanoquinone, oxone,dimyristoylphosphatidylinositol, and trifluoromethanesulfonimide. 13.The doped graphene film of claim 9, wherein the graphene film includes amonolayer graphene or a multilayer graphene.
 14. The doped graphene filmof claim 9, wherein the graphene film has a roll shape, a foil shape, atube shape, a plate shape, a sheet shape or a wire shape.
 15. A devicemanufactured by using a doped graphene film of claim
 9. 16. The deviceof claim 15, wherein the doped graphene film is manufactured by aroll-to-roll doping method of claims
 1. 17. A roll-to-roll dopingapparatus of a graphene film comprising: a first roller unit that formsa layered structure including a substrate-graphene film-first flexiblesubstrate; a second roller unit that removes the substrate from thelayered structure by immersing the layered structure provided by thefirst roller unit in an etching solution and transfers the graphene filmon the first flexible substrate at the same time; a third roller unitthat transfers the graphene film transferred on the first flexiblesubstrate on a second flexible substrate; and a fourth roller unit thatdopes the graphene film by passing the graphene film through a dopingsolution or a dopant vapor and that is placed between the second rollerunit and the third roller unit, or next to the third roller unit.